On-Demand Activation of Transesterification by Chemical Amplification in Dynamic Thiol-Ene Photopolymers.

Chemical amplification is a well-established concept in photoresist technology, wherein one photochemical event leads to a cascade of follow-up reactions that facilitate a controlled change in the solubility of a polymer. Herein, we transfer this concept to dynamic polymer networks to liberate both catalyst and functional groups required for bond exchange reactions under UV irradiation. For this, we exploit a photochemically generated acid to catalyse a deprotection reaction of an acid-labile tert-butoxycarbonyl group, which is employed to mask the hydroxy groups of a vinyl monomer. At the same time, the released acid serves as a catalyst for thermo-activated transesterifications between the deprotected hydroxy and ester moieties. Introduced in an orthogonally cured (450 nm) thiol-click photopolymer, this approach allows for a spatio-temporally controlled activation of bond exchange reactions, which is crucial in light of the creep resistance versus reflow ability trade-off of dynamic polymer networks.

Vat Photopolymerization 3D-Printing of Dynamic Thiol-Acrylate Photopolymers Using Bio-Derived Building Blocks.

As an energy-efficient additive manufacturing process, vat photopolymerization 3D-printing has become a convenient technology to fabricate functional devices with high resolution and freedom in design. However, due to their permanently crosslinked network structure, photopolymers are not easily reprocessed or repaired. To improve the environmental footprint of 3D-printed objects, herein, we combine the dynamic nature of hydroxyl ester links, undergoing a catalyzed transesterification at elevated temperature, with an acrylate monomer derived from renewable resources. As a sustainable building block, we synthesized an acrylated linseed oil and mixed it with selected thiol crosslinkers. By careful selection of the transesterification catalyst, we obtained dynamic thiol-acrylate resins with a high cure rate and decent storage stability, which enabled the digital light processing (DLP) 3D-printing of objects with a structure size of 550 µm. Owing to their dynamic covalent bonds, the thiol-acrylate networks were able to relax 63% of their initial stress within 22 min at 180 °C and showed enhanced toughness after thermal annealing. We exploited the thermo-activated reflow of the dynamic networks to heal and re-shape the 3D-printed objects. The dynamic thiol-acrylate photopolymers also demonstrated promising healing, shape memory, and re-shaping properties, thus offering great potential for various industrial fields such as soft robotics and electronics.